29 research outputs found
One-Pot Synthesis of 2,4-Disubstituted Thiazoline from β‑Azido Disulfide and Carboxylic Acid
A concise and efficient one-pot four-step synthesis of
2,4-disubstituted thiazoline via a cascade disulfide bond cleavage/thiocarbonylation/Staudinger
reduction/aza-Wittig reaction is established. Treatment of various
carboxylic acids with β-azido disulfides under this one-pot
procedure obtained the desired thiazolines in good to excellent isolated
yields
Total Synthesis of Tetracyclic Spirooxindole Alkaloids via a Double Oxidative Rearrangement/Cyclization Cascade
Skeleton rearrangement could rapidly
transfer simple molecules
to complex structures and has significant potential in the total synthesis
of natural products. We developed a one-pot reaction cascade of double
oxidative rearrangement of furan and indole followed by a nucleophilic
cyclization that was successfully applied for the formal synthesis
of rhynchophylline/isorhynchophylline and the first total synthesis
of (±)-7(R)-geissoschizol oxindole/(±)-7(S)-geissoschizol oxindole. In addition, the geissoschizol
oxindoles were revised to their C3 epimers, and the mechanism for
the reversed stereochemistry through the retro-Mannich/Mannich cascade
was proposed and supported by density functional theory calculations
Total Synthesis of Tetracyclic Spirooxindole Alkaloids via a Double Oxidative Rearrangement/Cyclization Cascade
Skeleton rearrangement could rapidly
transfer simple molecules
to complex structures and has significant potential in the total synthesis
of natural products. We developed a one-pot reaction cascade of double
oxidative rearrangement of furan and indole followed by a nucleophilic
cyclization that was successfully applied for the formal synthesis
of rhynchophylline/isorhynchophylline and the first total synthesis
of (±)-7(R)-geissoschizol oxindole/(±)-7(S)-geissoschizol oxindole. In addition, the geissoschizol
oxindoles were revised to their C3 epimers, and the mechanism for
the reversed stereochemistry through the retro-Mannich/Mannich cascade
was proposed and supported by density functional theory calculations
Total Synthesis of Tetrodotoxin and 9-epiTetrodotoxin
Tetrodotoxin and congeners are specific voltage-gated sodium channel blockers that exhibit remarkable anesthetic and an-algesic effects. Here, we present a scalable asymmetric synthesis of TTX and 9-epiTTX from the abundant chemical feed-stock furfuryl alcohol. The optically pure cyclohexane skeleton was assembled via a stereoselective Diels-Alder reaction. The dense heteroatom substituents were established sequentially by a series of functional group interconversions on highly oxygenated cyclohexane frameworks, including a chemoselective cyclic anhydride opening, and a decarboxylative hydrox-ylation. An innovative SmI2-mediated concurrent fragmentation, an oxo-bridge ring opening and ester reduction followed by an Upjohn dihydroxylation delivered the highly oxidized skeleton. Ruthenium-catalyzed oxidative alkyne cleavage and formation of the hemiaminal and orthoester under acidic conditions enabled the rapid assembly of TTX, anhydro-TTX, 9-epiTTX, and 9-epi lactone-TTX
Total syntheses of Tetrodotoxin and 9-epiTetrodotoxin
Abstract Tetrodotoxin and congeners are specific voltage-gated sodium channel blockers that exhibit remarkable anesthetic and analgesic effects. Here, we present a scalable asymmetric syntheses of Tetrodotoxin and 9-epiTetrodotoxin from the abundant chemical feedstock furfuryl alcohol. The optically pure cyclohexane skeleton is assembled via a stereoselective Diels-Alder reaction. The dense heteroatom substituents are established sequentially by a series of functional group interconversions on highly oxygenated cyclohexane frameworks, including a chemoselective cyclic anhydride opening, and a decarboxylative hydroxylation. An innovative SmI2-mediated concurrent fragmentation, an oxo-bridge ring opening and ester reduction followed by an Upjohn dihydroxylation deliver the highly oxidized skeleton. Ruthenium-catalyzed oxidative alkyne cleavage and formation of the hemiaminal and orthoester under acidic conditions enable the rapid assembly of Tetrodotoxin, anhydro-Tetrodotoxin, 9-epiTetrodotoxin, and 9-epi lactone-Tetrodotoxin
Chiral Allene-Containing Phosphines in Asymmetric Catalysis
We demonstrate that allenes, chiral 1,2-dienes, appended with basic functionality can serve as ligands for transition metals. We describe an allene-containing bisphosphine that, when coordinated to Rh(I), promotes the asymmetric addition of arylboronic acids to α-keto esters with high enantioselectivity. Solution and solid-state structural analysis reveals that one olefin of the allene can coordinate to transition metals, generating bi- and tridentate ligands
Chiral Allene-Containing Phosphines in Asymmetric Catalysis
We demonstrate that allenes, chiral 1,2-dienes, appended with basic functionality can serve as ligands for transition metals. We describe an allene-containing bisphosphine that, when coordinated to Rh(I), promotes the asymmetric addition of arylboronic acids to α-keto esters with high enantioselectivity. Solution and solid-state structural analysis reveals that one olefin of the allene can coordinate to transition metals, generating bi- and tridentate ligands